Effects of chain length on the size, stability, and electronic structure of redox-active organic–inorganic hybrid polyoxometalate micelles

Abstract

Double-chain redox-active surfactants based on hybrid polyoxometalates show solvent-dependent assembly into nanoscale micellar architectures.

Asymmetric Hybrid Polyoxometalates: A Platform for Multifunctional Redox‐Active Nanomaterials

“…Functionalization of polyoxotungstates with aryl phosphonate groups enhances their photochemical properties and can be employed to direct their self‐assembly into micellar superstructures . Here, we aimed to introduce two distinct, orthogonal functionalities via asymmetric functionalization and designed two suitable aryl phosphonates accordingly: (PO 3 C 21 H 16 N 3 ) (TPY), a terpyridine‐based ligand, and (PO 4 C 24 H 43 ) (C 18 ), an aliphatic chain group (see the Supporting Information).…”

“…Recently, we showed that self‐assembled micellar nanostructures formed from hybrid POM species exhibit different redox properties to their constituent molecular species . CV experiments were conducted on 1 dissolved in a 0.1 m H 2 SO 4 :CH 3 CN (9:1, v/v) mixture, allowing for spontaneous assembly into micellar species as described above.…”

Asymmetric Hybrid Polyoxometalates: A Platform for Multifunctional Redox‐Active Nanomaterials

“…Recently,w es howed that self-assembled micellar nanostructures formed from hybrid POM species exhibit different redox properties to their constituent molecular species. [29,35] CV experiments were conducted on 1 dissolved in a0 .1m H 2 SO 4 :CH 3 CN (9:1, v/v) mixture,a llowing for spontaneous assembly into micellar species as described above.Here,j ust two redox processes were observed between À0.5 and 0.5 V (vs.A g/AgCl) in contrast to the three seen in pure DMF (Supporting Information, Figure S15), as appears typical of micellar species of this type. [29,35] Notably,c haracteristic molecular redox behavior can be rapidly recovered by addition of DMF to the electrolyte solution, indicating the dynamic nature of this system and offering interesting potential for the development of responsive or switchable electrochemical devices.T his behavior also corresponds closely to that seen for our previously reported symmetric surfactant hybrid system, [35] and for the symmetric product 3 (Supporting Information, Figure S21).…”

“…Functionalization of polyoxotungstates with aryl phosphonate groups enhances their photochemical properties and can be employed to direct their self-assembly into micellar superstructures. [29,[34][35][36] Here,w ea imed to introduce two distinct, orthogonal functionalities via asymmetric functionalization and designed two suitable aryl phosphonates accordingly:( PO 3 C 21 H 16 N 3 )( TPY), at erpyridine-based ligand, and (PO 4 C 24 H 43 )( C 18 ), an aliphatic chain group (see the Supporting Information). Hybridization was then conducted based on the previously reported method.…”

Redox‐Active Hybrid Polyoxometalate‐Stabilised Gold Nanoparticles

“…[7,9] For example, it was recently shown that POMs could be functionalised with organophosphoryl groups to prepare a new family of amphiphilic hybrid POM surfactants. [10] The surfactant molecules self-assemble in solution to form micellar aggregates that retain the (modified) redox properties of the molecular building blocks, and similar nanoscale systems have been proposed as charge carriers for use in solution-phase energy-storage systems. [11] Hybrid POMs have also been used as capping agents for AuNPs, [12] whereby thiol-terminated organosilanefunctionalised clusters are used to covalently stabilise the NP surface.…”